The present invention relates to a process for the manufacture of 2-phenyl-4,5-oxazoledione 4-phenylhydrazone derivatives of formula (III), indicated below, which are useful as dyestuffs and also as intermediates of agrichemicals and pharmaceuticals
As shown in the below reaction scheme, 2-phenyl-4,5-oxazoledione 4-phenylhydrazone derivatives of the formula (III) are converted into triazole compounds of formula (IV) containing amide, acid, ester and ketone via reaction with nucleophilic reagent Nu--H, (referred to J. Am. Chem. Soc.,79, 1955-1956(1957), Heterocycle,20, 45-49(1983) and U.S. Pat. No. 4,795,484). ##STR1## wherein R.sup.1 is hydrogen, halogen, lower alkyl, lower alkoxy, lower alkylthio, lower alkoxycarbonyl, lower alkyl substituted with one or more halogen(s), cyano, nitro or AOCH.sub.2 ;
A is hydrogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkylalkyl, unsubstituted or substituted aryl, unsubstituted or substituted aralkyl,
R.sup.2 is hydrogen, halogen or lower alkyl;
R.sup.3 is hydrogen, halogen or lower alkyl;
R.sup.2 and R.sup.3 are the same or different;
R.sup.4 is hydrogen, halogen, lower alkyl, lower alkoxy, nitro, lower alkyl substituted with one or more halogen(s) or A'OCH.sub.2 ;
A' is alkyl substituted with one or more fluoro;
R.sup.5 is hydrogen, halogen, lower alkyl or lower alkoxy;
Nu--H (or Nu--) means so-called nucleophilic reagent including NH.sub.3, primary amine, secondary amine, hydroxy ion, alkoxy ion, hydrazine, hydroxyamine, carbanion from active methylene compound and the like.
U.S. Pat. Re 33,132 discloses a trizole carboxyamide of formula (A), preparation process thereof and herbicidal compositions. ##STR2## wherein R.sup.1 a is C.sub.1 -C.sub.3 alkyl, chloro, fluoro, iodo, trifluoromethyl or nitro
R.sup.2 a is hydrogen, methyl or chloro;
R.sup.3 a is hydrogen or methyl;
R.sup.4 a is hydrogen;
R.sup.5 a is hydrogen.
U.S. Pat. No. 4,795,484 (corresponding to JP 185572(1983) and JP 98004(1984)) discloses a triazole carboxamide of formula (B), preparation process thereof and herbicidal compositions. ##STR3## (wherein R.sup.1 b is hydrogen, halogen, C.sub.1 -C.sub.2 alkyl, fluoromethyl, 3,3,3-trifluoropropyl, methoxy, cyano, methoxymethyl, methylthio, methoxycarbonyl or (1-methylethyloxy)carbonyl;
R.sup.2 b is hydrogen, halogen, C.sub.1 -C.sub.2 alkyl;
R.sup.3 b is hydrogen;
R.sup.4 b is hydrogen;
R.sup.5 b is hydrogen;
Nub is aminocarbonyl, hydrazinocarbonyl, hydroxyaminocarbonyl, methoxyaminocarbonyl and the like.
JP 98004(1984) (corresponding to post-examination publication JP 60824(1991)) which is incorporated herein by reference discloses a triazole carboxamide of formula (C), preparation process thereof and herbicidal compositions. ##STR4## (wherein R.sup.1 c is hydrogen, halogen, C.sub.1 -C.sub.4 alkyl, halogeno (C.sub.1 -C.sub.4) alkyl, methoxy, methoxymethyl, methylthio, cyano or (C1-C4 alkoxy)carbonyl;
R.sup.2 c is hydrogen, halogen or C.sub.1 -C.sub.4 alkyl;
R.sup.3 c is hydrogen;
R.sup.4 c is hydrogen, C.sub.1 -C.sub.4 alkyl, halogen or halogeno (C.sub.1 -C.sub.4) alkyl;
R.sup.5 c is hydrogen;
Nuc is aminocarbonyl, hydrazinocarbonyl, hydroxyaminocarbonyl, methoxyaminocarbonyl and the like.) JP 98004 is the publication number of Japanese application number 57-206486 which is a priority document upon which U.S. Pat. No. 4,795,484 is based. U.S. Pat. No.4,795,484 discloses a herbicidal composition comprising a derivative of 1,2,4-triazole as an active ingredient, represented by the general formula (I): ##STR5## wherein R.sup.1 represents a hydrogen atom, a halogen atom or a (C.sub.1 -C.sub.2) alkyl group; R.sup.2 represents a hydrogen atom, a halogen atom, a (C.sub.1 -C.sub.2) alkyl group, fluoromethyl-methyl group (--CH.sub.2 F), 3,3,3-trifluoropropyl group, methoxy group, cyano group, methoxymethyl group, methylthio group, methoxycarbonyl group or isopropoxycarbonyl group and R.sup.3 represents a thiocarbamoyl group or a group represented by the formula (II): ##STR6## wherein R.sup.4 represents a hydrogen atom, a (C.sub.1 -C.sub.2) alkyl group or a hydroxy (C.sub.1 -C.sub.2) alkyl group and R.sup.5 represents a hydrogen atom, a (C.sub.1 -C.sub.2) alkyl group, halogeno (C.sub.1 -C.sub.2) alkyl group, hydroxy (C.sub.1 -C.sub.2) alkyl group, cyanomethyl group, acetyl group, halogenoacetyl group, methoxyacetyl group, amino group, phenyl group, methoxy group, hydroxyl group, (C.sub.2 -C.sub.3) alkenyl group, halogeno (C.sub.2 -C.sub.3) alkenyl group, isopropyl-carbonyl group, methylthiocarbamoyl group or 2-methoxyethyl group, with the proviso that R.sup.2 is not a hydrogen atom, halogen atom or (C.sub.1 -C.sub.2) alkyl group when both of R.sup.4 and R.sup.5 represent hydrogen atoms, and herbicidally acceptable carrier(s) or diluent(s).
The inventors of U.S. Pat. No. 4,795,484 sought a compound showing excellent activity in selectively controlling weeds such as Echinochloa crus-galli, Poa annua, Chenopodium album, Cardamine flexuosa, Portulaca orelacea, etc. Without any phytotoxicity to crop plants such as rice, wheat and maize, and as a result, they have found that a derivative of 1,2,4-triazole represented by the formula (I) shows an excellent herbicidal activity for practically controlling the weeds.
U.S. Pat. No. 4,820,334 discloses a triazole carboxamide of formula (D), preparation process thereof and herbicidal compositions. ##STR7## (wherein R.sup.1 d is 3-AdOCH.
Ad is hydrogen, straight or branched saturated (C.sub.2 -C.sub.10) alkyl which is unsubstituted or fluoro(s) substituted;
cyclic saturated (C.sub.3 -C.sub.10) alkyl which is unsubstituted or fluoro(s) substituted; PA1 (C.sub.1 -C.sub.8) alkoxy (C.sub.2 -C.sub.10) alkoxy (C.sub.2 -C.sub.10) alkyl; or a group of formula (D2), wherein p is an integer of 1-8; ##STR9## R.sup.2 d is hydrogen; R.sup.3 d is hydrogen; PA1 R.sup.4 d is hydrogen; PA1 R.sup.5 d is hydrogen. PA1 C.sub.3 -C.sub.10 cycloalkyl, (C.sub.4 -C.sub.10) cycloalkylalkyl, unsubstituted or halo substituted phenyl, C.sub.7 -C.sub.9 aralkyl, (C.sub.3 -C.sub.6) alkenyl, F.sub.1 -F.sub.19 substituted (C.sub.2 -C.sub.10) alkyl; PA1 R.sup.2 f is halogen or C.sub.1 -C.sub.3 alkyl; PA1 R.sup.3 f is hydrogen, halogen or C.sub.1 -C.sub.3 alkyl; PA1 R.sup.4 f is hydrogen or fluoro; PA1 R.sup.5 f is hydrogen or fluoro. PA1 R.sup.2 g is hydrogen; PA1 R.sup.3 g is hydrogen; PA1 R.sup.4 g is hydrogen; PA1 R.sup.5 g is hydrogen. PA1 R.sup.3 h is hydrogen; PA1 R.sup.4 h is 3-A'hOCH.sub.2 ; PA1 A'h is fluoro(s) substituted C.sub.2 -C.sub.10) alkyl; PA1 R.sup.5 h is hydrogen. PA1 R.sup.3 i is hydrogen; PA1 R.sup.4 i is alkyl, alkoxy, nitro or halogen; PA1 R.sup.5 i is hydrogen or the same as R.sup.4 i. PA1 optionally halo substituted (C.sub.1 -C.sub.4) alkoxy, PA1 optionally halo substituted (C.sub.1 -C.sub.4) alkylthio, PA1 optionally (C.sub.1 -C.sub.4) alkyl substituted (C.sub.3 -C.sub.6) cycloalkyl, hydroxymethyl, PA1 optionally (C.sub.1 -C.sub.4) alkyl substituted (C.sub.1 -C.sub.4 alkoxy) methyl, PA1 optionally one or more halogeno(s) and/or trifluoromethyl substituted phenyl and the like; PA1 R.sup.2 j is hydrogen or the same as R.sup.1 j; PA1 R.sup.3 j is hydrogen or the same as R.sup.1 j; PA1 R.sup.4 j is hydrogen, halogen, nitro, cyano, PA1 optionally halo substituted (C.sub.1 -C.sub.4) alkyl, PA1 optionally halo substituted (C.sub.1 -C.sub.4) alkoxy, PA1 optionally halo substituted (C.sub.1 -C.sub.4) alkylthio, PA1 optionally (C.sub.1 -C.sub.4) alkyl substituted (C.sub.3 -C.sub.6) cycloalkyl, hydroxymethyl, PA1 optionally (C.sub.1 -C.sub.4) alkyl substituted (C.sub.1 -C.sub.4 alkoxy) methyl, optionally one or more halogeno(s) and/or trifluoromethyl substituted phenyl and the like; PA1 R.sup.5 j is hydrogen or the same as R.sup.4 j; PA1 Nuj is hydroxy, C.sub.1 -C.sub.4 alkoxy and the like.
straight, branched or cyclic unsaturated (C.sub.3 -C.sub.10) alkyl which is unsubstituted or fluoro (s) substituted;
a group of formula (D1), wherein R.sup.6 d is halogen, C.sub.1 -C.sub.3 alkyl,
C.sub.1 -C.sub.3 alkoxy or fluoro (C.sub.1 -C.sub.3) alkyl, m is an integer of 0-5 and n is 0 or 1; ##STR8##
straight or branched saturated (C.sub.1 -C.sub.8) alkoxy (C.sub.2 -C.sub.10) alkyl; straight or branched unsaturated (C.sub.1 -C.sub.8) alkoxy (C.sub.2 -C.sub.10) alkyl; phenoxy (C.sub.2 -C.sub.6) alkyl; aralkoxy (C.sub.2 -C.sub.6) alkyl;
phenoxy (C.sub.2 -C.sub.6) alkyl having phenyl(s) substituted halogen(s) or C.sub.1 -C.sub.3 alkyl(s);
aralkoxy (C.sub.3 -C.sub.6) alkyl having phenyl(s) substituted halogen(s) or C.sub.1 -C.sub.3 alkyl(s);
U.S. Pat. No. 4,919,707 discloses a triazole carboxamide of formula (E) , preparation process thereof and herbicidal compositions. ##STR10## wherein R.sup.1 e is 3-AeOCH.sub.2 ;
A.sup.e is straight (C.sub.2 -C.sub.10) alkyl, branched (C.sub.3 -C.sub.10) alkyl,
R.sup.2 e is hydrogen;
R.sup.3 e is hydrogen;
R.sup.4 e is fluoro, chloro, methyl or methoxy;
R.sup.3 e is hydrogen.
U.S. Pat. No. 4,973,353 discloses a triazole carboxamide of formula (F), preparation process thereof and herbicidal compositions. ##STR11## wherein R.sup.1 is 3-AfOCH.sub.2 ;
Af is unsubstituted or F.sub.1 -F.sub.19 substituted straight (C.sub.1 -C.sub.10) alkyl, unsubstituted or F.sub.1 -F19 substituted branched (C.sub.3 -C.sub.10) alkyl, (C.sub.3 -C.sub.10) cycloalkyl, (C.sub.3 -C.sub.7) cycloalkyl (C.sub.1 -C.sub.3) alkyl, phenyl or C.sub.7 C.sub.9 aralkyl;
U.S. Pat. No. 5,001,275 discloses a triazole carboxamide of formula (G) , preparation process thereof and herbicidal compositions. ##STR12## wherein R.sup.1 g is 3-AgOCH.sub.2 ; Ag is branched (C.sub.4 -C.sub.8) alkyl, (C.sub.4 -C.sub.8) cycloalkyl, (C.sub.3 -C.sub.7) cycloalkyl (C.sub.1 -C.sub.3) alkyl, C.sub.7 -C.sub.9 aralkyl, (C.sub.1 -C.sub.4) alkoxy (C.sub.2 -C.sub.4) alkyl, unsaturated (C.sub.3 -C.sub.6) alkyl, F.sub.1 -F.sub.15 substituted straight (C.sub.2 -C.sub.8) alkyl, F.sub.1 -F.sub.15 substituted branched (C.sub.3 -C.sub.8) alkyl,
U.S. Pat. No. 5,094,684 (corresponding to EP 297734) discloses a triazole carboxamide of formula (H), preparation process thereof and herbicidal compositions. ##STR13## wherein R.sup.1 h is hydrogen or fluoro; R.sup.2 h is hydrogen;
JP 58-185572; Chem. Abstr., 100, 156607X(1984) which is incorporated herein by reference discloses a triazole carboxamide of formula (II), preparation process thereof and herbicidal compositions. ##STR14## wherein R.sup.1 i is hydrogen or alkyl; R.sup.2 i is hydrogen or the same as R.sup.1 i;
The aforementioned Chemical Abstracts reference discloses compounds of the formula ##STR15## wherein R is hydrogen or alkyl; R.sup.1 is alkyl or alkoxy, m=0-2 and n=1-2. The compounds of formula I of the reference were shown to have herbicidal activity against Echochloa crus-galli, Chenopodium album, Portulaca oleracea, and the like.
EP 346620 which is incorporated herein by reference discloses a triazole compound of formula (J), preparation process thereof and safener compositions for herbicide. ##STR16## wherein R.sup.1 j is hydrogen, halogen, nitro, cyano, optionally halo substituted (C.sub.1 -C.sub.4) alkyl,
EP 346 620 further discloses 1,2,4-triazole derivatives of the formula: ##STR17## wherein Z or Z.sub.1 are halogen, nitro, cyano, or an amino, alkyl, alkoxy, alkylthio, cycloalkyl, phenyl, or phenoxy, and X is hydroxy, --OCH.sub.2 Si(CH).sub.3, alkyl, cycloalkoxy, phenoxy, alkenyloxy, alkynyloxy, substituted alkoxy, or substituted alkylthio. The compounds are indicated to be useful as safeners for herbicides.
U.S. Pat. No. 4,820,334 and EP 346620 do not use 2-phenyl-4,5-oxazoledione 4-phenylhydrazone derivatives as precursors. But, the triazole carboxamide of formula (D) and the triazole compound of formula (J) can be also prepared via the reaction of the corresponding 2-phenyl-4,5-oxazoledione 4-phenylhydrazone derivatives and nucleophilic reagents. (referred to J. Am. Chem. Soc., 79, 1955-1956(1957) and Heterocycle, 20, 45-49(1983)).
Prior to the present invention, it had been thought that 2-phenyl-5(4H)-oxazolone derivatives were the precursors in the step of diazo coupling for preparation of 2-phenyl-4,5-oxazoledione 4-phenylhydrazone derivatives, and 2-phenyl-5(4H)-oxazolone derivatives had to be prepared before use via rapidly heating of hippuric acids and acetic anhydride in the condition free from water and then rapidly cooling. Further, a person skilled in the art knows that 2-phenyl-5(4H)-oxazolone derivatives are unstable not only in the cyclocondensed mixture of hippuric acids and acetic anhydride but also in an aqueous acidic mixture (referred to Org. Syn. Coll., 5,946-948(1973) and J. Am. Chem. Soc., 102, 6828-6837(1980)). For example, as shown in FIG. 2 on page 6830 of the above JACS(1980), half-life period of 2-(4-chlorophenyl)-5(4H)-oxazolone in pH 1-2 is about 7 seconds. Accordingly, it is unexpected that hippuric acids and acetic anhydride could be used in the step of diazo coupling instead of the freshly prepared 2-phenyl-5(4H)-oxazolone derivatives.